EP0345552A2 - Copolymères contenant des groupes perfluoralkyl - Google Patents

Copolymères contenant des groupes perfluoralkyl Download PDF

Info

Publication number
EP0345552A2
EP0345552A2 EP89109459A EP89109459A EP0345552A2 EP 0345552 A2 EP0345552 A2 EP 0345552A2 EP 89109459 A EP89109459 A EP 89109459A EP 89109459 A EP89109459 A EP 89109459A EP 0345552 A2 EP0345552 A2 EP 0345552A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
aqueous dispersions
weight
parts
graft
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89109459A
Other languages
German (de)
English (en)
Other versions
EP0345552B1 (fr
EP0345552A3 (fr
Inventor
Carlhans Dr. Süling
Jutta Dr. Röttger
Henning Dr. Bachem
Joachim Dr. Probst
Wilfried Dr. Kortmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0345552A2 publication Critical patent/EP0345552A2/fr
Publication of EP0345552A3 publication Critical patent/EP0345552A3/fr
Application granted granted Critical
Publication of EP0345552B1 publication Critical patent/EP0345552B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine

Definitions

  • the invention relates to aqueous dispersions of copolymers and graft copolymers of ethylenically unsaturated perfluoroalkyl monomers and perfluoroalkyl group-free ethylenically unsaturated monomers which are prepared in the presence of emulsifiers containing cationic groups, a process for their preparation and their use for the hydrophobization and oleophobicization of textiles, leather and paper.
  • Copolymer dispersions based on monomers containing perfluoroalkyl groups in water are known. They provide good oleophobic finishes on many substrates if the perfluoroalkyl residues are linear and contain more than 6 carbon atoms in the perfluoroalkyl residue.
  • Emulsifiers or emulsifier systems are used in the preparation of these copolymer dispersions by emulsion polymerization. Depending on the emulsifier system, anionically or cationically stabilized is obtained Dispersions, the shelf life of which can be improved by adding nonionic emulsifiers. Cationic polyperfluoroalkyl (meth) acrylate copolymer dispersions are particularly suitable for textile and carpet oleophobization, also in conjunction with other finishing agents or textile auxiliaries.
  • oleophobicizing agents based on polyperfluoroalkyl (meth) acrylate dispersions is essentially dependent on the concentration of perfluoroalkyl groups in the copolymer, on the composition of the copolymer and its particle size.
  • the type of emulsifiers used also influences the performance properties. From an application point of view, it is often necessary for the oleophobic finish to additionally cause hydrophobization.
  • the emulsifiers are often one of the reasons why the finished goods have a high dirt retention capacity.
  • the task then arises to develop emulsifier systems which allow the production of very fine-particle perfluoroalkyl polymer dispersions and their effectiveness as Do not adversely affect water repellents and their soiling behavior.
  • Fine-particle dispersions are understood to mean dispersions with average particle sizes below 600 nm. Particularly good results are obtained if dispersions with average particle sizes of 200 to 500 nm are used.
  • R2 and R3 independently of one another for methyl or ethyl, R4 for C1-C6 alkyl, benzyl, phenylethyl or cyclohexyl or a radical of the formula -CH2- -CH2-Q R5 represents hydrogen or C1-C8-alkyl, R6 for C15-C22-alkyl and W ⁇ for Cl ⁇ , Br ⁇ , 1/2 SO42 ⁇ , 1/3 PO43 ⁇ , CH3-O-SO3 ⁇ or CH3-COO ⁇ .
  • the cationic emulsifiers of the general formula (I) are water-soluble compounds. They are by free-radical copolymerization of styrene and its derivatives, (meth) acrylonitrile, (meth) acrylic acid and its esters with dialkylaminoalkyl (meth) acrylates or dialkylaminoalkyl (meth) acrylamides in solution, dispersion or mass and subsequent quaternization available, the degree of quaternization is at least 10%.
  • a preferred embodiment is the polymerization of the monomer mixtures in solution with subsequent quaternization.
  • Conventional peroxidic starters or aliphatic azo compounds can be used as initiators. It is advantageous to use solvents in solution polymerization which do not have too high transfer constants, e.g. Butanol, isopropanol, acetone, methyl isobutyl ketone or alkyl acetate.
  • Derivatives containing tertiary amino groups are preferably used as aminoalkyl (meth) acrylates.
  • Examples include diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide and dimethylaminoethyl (meth) acrylate.
  • Preferred polymers (I) are made from these basic monomers and (meth) acrylic acid alkyl esters with 1-4 C atoms in the alkyl radical and / or (meth) acrylic acid alkyl esters with 8 to 22 C atoms in the alkyl radical in approximately equimolar amounts or from these basic monomers , Styrene and acrylonitrile in the ratio of 1 to 2, 2 to 10 and 1 to 1.5 obtained.
  • the quaternization of the basic polymers can be carried out using known quaternizing agents such as alkyl halides, dialkyl sulfates and monoepoxides and is carried out in a manner known per se (for example according to EP-A 0 160 872).
  • the quaternizing agent is used in a molar ratio of 0.25-2.5, preferably 0.5-2.0, based on mole of basic nitrogen in the preliminary product.
  • the optionally remaining tertiary amino groups are protonated.
  • Preferred ethylenically unsaturated perfluoroalkyl monomers are those of the formulas wherein R1 is hydrogen or methyl, R7 C1-C4 alkyl, m 1 or 2 and n mean 6-12.
  • ethylenically unsaturated monomers which are used in addition to the perfluoroalkyl monomers for the preparation of the polymer dispersions according to the invention, depends on the particular application requirements.
  • these comonomers are styrene, acrylic and methacrylic acid esters, vinyl esters such as vinyl acetate, maleic acid derivatives and acrylic or methacrylamides.
  • perfluoroalkyl monomers of the formulas (II) and / or (III) using the emulsifiers (I) according to the invention are copolymerized with monomer mixtures comprising at least one mixture component of the formula wherein R8 for hydrogen, methyl or fluorine and R9 represents a C8-C22-alkyl radical, contain.
  • Examples of comonomers of the general formula (IV) are acrylic acid or methacrylic acid esters of behenyl alcohol, stearyl alcohol, oleyl alcohol, nonyl alcohol or octyl alcohol or isomer mixtures of such alcohols.
  • esters (IV) can be copolymerized in a mixture with the above-mentioned fluorine-free monomers, for example also with esters of acrylic and methacrylic acid and C1-C7 alkanols.
  • water-insoluble comonomers are preferred, albeit, for example, to ensure a certain degree of adhesion to the various substrates Oleophobic / hydrophobic armor in proportions up to 10%, preferably 2%, water-soluble comonomers can be used.
  • auxiliary solvents are solvents which have little influence on the course of the emulsion polymerization, e.g. Alcohols such as methanol, ethanol, n-propanol, isopropanol and tert-butanol, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and amides such as dimethylacetamide.
  • auxiliary solvent water which is immiscible or only miscible with water, such as esters of lower alcohols with lower carboxylic acids, provided that no ester saponification can take place under the conditions of the emulsion polymerization.
  • ethyl acetate, methyl acetate, methyl propionate or methyl ethyl ketone is particularly advantageous.
  • the auxiliary solvent is removed after the polymerization is complete.
  • the emulsions are produced in stirring units, ultrasound apparatus or homogenizers.
  • radical binders e.g. aliphatic azo compounds such as azodiisobutyronitrile and organic or inorganic peroxides are suitable.
  • Organic peroxides which may be mentioned are diacyl peroxides such as dibenzoyl peroxide, hydroperoxides such as tert-butyl hydroperoxide, tert-butyl perpivalate and percarbonates such as dicyclohexyl percarbonate.
  • the alkali metal salts of peroxidic sulfuric acid are particularly suitable as inorganic peroxides.
  • the polymerization temperatures are up to 100 ° C, preferably 50-100 ° C, in particular 60-90 ° C.
  • Suitable starter systems are e.g. Mixtures of peroxidisulfates and reducing sulfur compounds such as bisulfites or thiosulfates or combinations of diacyl peroxides with tert. Amines.
  • the known chain transfer agents based on mercapto compounds or aliphatic aldehydes can be used to adjust the molecular weights or the molecular weight distributions.
  • a graft polymerization can take place at the same time, in which portions of the copolymer are grafted onto the cationic emulsifier (I).
  • copolymer dispersions according to the invention are graft copolymer dispersions which are prepared using known graft bases. Graft copolymerization using perfluoroalkyl (meth) acrylates in an aqueous emulsion is known. It is e.g. in German Offenlegungsschriften 3 407 361 and 3 407 362. Particularly suitable graft bases are hydrophobic polymers in the form of aqueous dispersions. Particularly good application results are obtained if the graft bases themselves have the properties of water repellents.
  • cationic and / or nonionic emulsifiers in addition to the cationic emulsifiers (I).
  • cationic emulsifiers are quaternary ammonium or pyridinium salts, for example stearyldimethylbenzylammonium chloride or N, N, N-trimethyl-N-perfluorooctanesulfonamidopropylammonium chloride.
  • the stability of the copolymer dispersions is increased in particular by nonionic emulsifiers.
  • nonionic emulsifiers are polyglycol ethers, e.g. Ethylene oxide / propylene oxide block or copolymers and alkoxylation products, in particular ethoxylation products of fatty alcohols, alkylphenols, fatty acids, fatty acid amides, sorbitol monooleate.
  • cationic emulsifiers In the preparation of the polymer dispersions, based on the amounts of monomers used for the polymerization, 0.1 to 7% by weight, preferably 0.2-4% by weight, of the cationic emulsifiers according to the invention are used. Of the usual cationic emulsifiers, 1-5% by weight, preferably 1.2-3% by weight, can be used. The known nonionic emulsifiers are advantageously used in amounts of 1-5% by weight, preferably 1.5-4.5% by weight. In the preparation of copolymer dispersions with particularly advantageous performance properties, it is necessary to use emulsifier systems which contain the different types of emulsifiers described in approximately equal amounts. The total amount of all emulsifiers should not exceed 10% by weight.
  • the finishing is carried out by known methods, preferably by the pull-out or padding method, for example between room temperature and 40 ° C., but also by splashing or spraying with a subsequent temperature treatment at 80-180, preferably 120 to 150 ° C.
  • tert-Butanol are 100 parts by weight in a reactor Dimethylaminoethyl methacrylate and 100 parts by weight Stearyl methacrylate dissolved. After displacing the atmospheric oxygen, 4 parts by weight are added. Azodiisobutyronitrile (AIBN) too. The reactor is heated to 70 ° C. and kept at this temperature for 7 hours with stirring. After cooling, a monomer conversion of> 96% is found by a solid determination.
  • AIBN Azodiisobutyronitrile
  • the monoepoxide (V) as quaternizing agent in about 15 min. metered in and stirred for about 1 hour.
  • the remaining amount of acetic acid (VI) is then added.
  • Approx. 63 - 65 l of deionized water at a temperature of approx. 60 ° C. are placed in a 120 l storage vessel equipped with a stirrer and the contents of the 40 l autoclave are combined with it.
  • a homogeneous aqueous solution is prepared in a short time with vigorous stirring.
  • the aqueous solutions which still contain organic solvent have the properties also listed in Table 1.
  • Azoisobutyronitrile (g) 500 500 550 500 500 Acetone (g) 3000 3000 3000 3000 3000 III.
  • Azoisobutyronitrile (g) 50 50 50 50 50 50 Acetone (g) 300 300 300 300 300 IV.
  • Acetic acid (g) 1229 984 690 984 984 V.
  • 1,2-epoxydodecane (g) 1131 - - - - 1,2-epoxyhexane (g) - 1025 719 - - 1,2-epoxybutane (g) - - - 885 - Propylene oxide (g) - - - - 891 VI.
  • Viscosity is not constant because samples are pseudoplastic
  • Solution 1 600 Parts by weight deionized water 2.75 Parts by weight Benzyldodecyldimethylammonium chloride 18.45 Parts by weight the emulsifier solution obtained according to Example 2a
  • Solution 2 247 Parts by weight Ethyl acetate 30.8 Parts by weight N-methyl-N-perfluorooctanesulfonamidoethyl methacrylate 42.6 Parts by weight
  • Solution 3 1,125 Parts by weight t-butyl perpivalate 1.5 Parts by weight Ethyl acetate
  • Solutions 1 and 2 are used to produce a mixture which is emulsified to constant particle size at 40 ° C. in an emulsifying machine.
  • the emulsion obtained is placed in a reactor equipped with a stirrer, reflux condenser and internal thermometer.
  • Solution 3 is added at 40 ° C. and stirred for 15 minutes.
  • the temperature is then increased to 70 ° C. and this value is maintained for 2 hours.
  • the temperature is then increased again and kept in the range of 70-80 ° C. for 2 hours, so that the ethyl acetate can distill off using an additional distillation bridge.
  • the mixture is stirred for a further hour at 80 ° C.
  • Example 5 The procedure is as in Example 5, but in solution 1 the emulsifier solution obtained according to example 2a is replaced by 14 parts by weight of an emulsifier solution obtained according to example 3E (see table 1). Solids content: 15.4% Fluorine content in the solid: 14.6% Average particle size: 476 nm (after light scattering)
  • a copolymer dispersion is prepared as described in Example 5, but with the solution from Example 2a omitted. Solids content: 13.7% Fluorine content in the solid: 15.4% Average particle size: 327 nm (after light scattering)
  • Solution 1 760 Parts by weight deionized water 4.5 Parts by weight an ethoxylated nonylphenol with 10 EO 9.2 Parts by weight the emulsifier solution obtained according to Example 2b
  • Solution 2 300 Parts by weight Ethyl acetate 55.6 Parts by weight N-methyl-N-perfluorooctanesulfonamidoethyl methacrylate 29.5 Parts by weight Stearyl methacrylate 23.8 Parts by weight Vinyl acetate 22.8 Parts by weight Graft base obtained as in Example 4
  • a mixture is prepared from solutions 1 and 2, which is emulsified at 50 ° C. in an emulsifying machine.
  • the emulsion obtained is placed in a reactor equipped with a stirrer, reflux condenser and internal thermometer and allowed to cool to 30 ° C.
  • Solution 3 to 30 ° C. is added with stirring.
  • the temperature is raised from 30 to 50 ° C. in 1 hour and from 50 to 70 ° C. in a further hour.
  • the reaction mixture is then left under stirring at 70 ° C. for 2 hours.
  • Solution 1 760 Parts by weight deionized water 4.54 Parts by weight an ethoxylated nonylphenol 10 EO 1.8 Parts by weight Benzyldodecyldimethylammonium chloride
  • Solution 2 300 Parts by weight Ethyl acetate 55.6 Parts by weight N-methyl-N-perfluorooctanesulfonamidoethyl methacrylate 29.5 Parts by weight Stearyl methacrylate 23.8 Parts by weight Vinyl acetate 22.8 Parts by weight Graft base obtained as in Example 4
  • Solution 3 1,018 Parts by weight t-butyl perpivalate 1,429 Parts by weight Dilauroyl peroxide 8.1 Parts by weight Ethyl acetate
  • a mixture is prepared from solutions 1 and 2 and this is emulsified at 50 ° C. in an emulsifying machine.
  • the emulsion obtained is placed in a reactor equipped with a stirrer, reflux condenser and internal thermometer and allowed to cool to 30 ° C.
  • Solution 3 to 30 ° C. is added with stirring and the temperature is raised from 30 to 50 ° C. within 1 hour and from 50 to 70 ° C. in a further hour.
  • the reaction mixture is then left at 70 ° C. for 2 hours.
  • the temperature is then kept at 70-80.degree. C. for 3 hours and the ethyl acetate is distilled off using an additional distillation bridge.
  • Solids content 13.1% Fluorine content in the solid: 26.7% Average particle size: 270 nm (after light scattering)
  • Tables 1 and 2 show the performance results obtained when the copolymer dispersions prepared according to Examples 5 to 9 are used in the oleophobic / hydrophobic finishing of carpets based on synthetic polyamide fibers.
  • Table 1 Oleohobia 1) Hydrophobicity 2) Example 5 4-5 50/50 Example 6 6 30/70 Example 7 3rd 60/40 / -70 / 30 1) According to AATCC test method 118 2) Resistance to aqueous isopropanol solutions according to the standard method.
  • the polymerization according to the invention is also superior in this comparison.
  • Solution 1 800 Parts by weight deionized water 5 Parts by weight ethoxylated nonylphenol with an average of 10 ethylene oxide units 6.9 Parts by weight Benzyldodecyldimethylammonium chloride 17.3 Parts by weight the emulsifier solution obtained according to Example 2c Solution 2: 402 Parts by weight Ethyl acetate 43.5 Parts by weight Dioctyl adipate 54.2 Parts by weight N-methyl-N-perfluorooctanesulfonamidoethyl methacrylate 24.9 Parts by weight Stearyl methacrylate 1.44 Parts by weight Isobutyl methacrylate
  • Solution 3 0.9 Parts by weight t-butyl perpivalate 2.1 Parts by weight Ethyl acetate 0.9 Parts by weight Didecanoyl peroxide
  • a mixture is prepared from solutions 1 and 2 and this is emulsified five times at 50 ° C. in an emulsifying machine.
  • the emulsion obtained is placed in a reactor equipped with a stirrer, reflux condenser and internal thermometer.
  • Solution 3 is added with stirring at 50.degree.
  • the mixture is stirred for a further half an hour at 50 ° C., then the temperature is raised from 50 to 70 ° C. within 1 hour and then kept at 70 ° C. for 2 hours.
  • the reaction mixture is then allowed to react at reflux (at about 70 ° C.) for 3 hours.
  • a preliminary latex with a solids content of 10.4% is obtained.
  • Solution 1 1365 Parts by weight Pre-latex from level 1 34.3 Parts by weight Ethyl acetate 45.3 Parts by weight Isobutyl methacrylate 2.8 Parts by weight N-methyl-N-perfluorooctanesulfonamidoethyl methacrylate
  • Solution 2 0.943 Parts by weight t-butyl perpivalate 1.75 Parts by weight Ethyl acetate 0.48 Parts by weight Didecanoyl peroxide
  • Solution 1 is emulsified at 50 ° C in an emulsifying machine and then placed in a reactor with stirrer, reflux condenser and internal thermometer.
  • Solution 2 is added with stirring at 50 ° C. and everything is stirred at 50 ° C. for half an hour.
  • the mixture is then heated from 50 to 70 ° C. within 1 hour and kept at 70 ° C. for a further 2 hours.
  • the mixture is then run for a further 2 hours at 70-80 ° C. and the ethyl acetate is distilled off using an additional distillation device. Finally, stirring is continued at 80 ° C. for 1 hour.
  • Example 10 The procedure is as in Example 10, but in order to prepare the preliminary latex (1st stage) in solution 1, the emulsifier solution obtained according to Example 2c is replaced by 17.3 parts by weight of an emulsifier solution obtained according to Example 3E (see table). Solids content: 23.2% Fluorine content in the solid: 14.4%
  • Unstable polymer dispersions are obtained without the addition of an emulsifier (I) before the emulsion polymerization.
  • the grade for the oleophobia was 3-4 for Example 10 and 6 for Example 11 and for Example 10 the values 60/40 to 70/30 and for Example 11, respectively the value 70/30 for hydrophobicity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
EP89109459A 1988-06-08 1989-05-25 Copolymères contenant des groupes perfluoralkyl Expired - Lifetime EP0345552B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3819476 1988-06-08
DE3819476 1988-06-08
DE3842539A DE3842539A1 (de) 1988-06-08 1988-12-17 Perfluoralkylgruppen enthaltende copolymerisate
DE3842539 1988-12-17

Publications (3)

Publication Number Publication Date
EP0345552A2 true EP0345552A2 (fr) 1989-12-13
EP0345552A3 EP0345552A3 (fr) 1991-03-27
EP0345552B1 EP0345552B1 (fr) 1993-11-18

Family

ID=25868919

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89109459A Expired - Lifetime EP0345552B1 (fr) 1988-06-08 1989-05-25 Copolymères contenant des groupes perfluoralkyl

Country Status (4)

Country Link
US (1) US4997873A (fr)
EP (1) EP0345552B1 (fr)
JP (1) JPH0243210A (fr)
DE (2) DE3842539A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0572269A1 (fr) * 1992-05-29 1993-12-01 Hoechst Gosei K.K. Composition aqueuse contenant du fluor, ayant des propriétés oléophobes et hydrophobes

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3934543A1 (de) * 1989-10-17 1991-04-18 Bayer Ag Perfluoralkylgruppen enthaltende copolymerisate/ii
US5139376A (en) * 1991-10-23 1992-08-18 Excellon Automation Method and apparatus for controlled penetration drilling
US5332340A (en) * 1992-07-27 1994-07-26 Excellon Automation Drilling method and apparatus using variable dwell times
US5714082A (en) * 1995-06-02 1998-02-03 Minnesota Mining And Manufacturing Company Aqueous anti-soiling composition
US5807035A (en) * 1995-10-20 1998-09-15 Lewin; Howard S. Clamp for drill press
DE69606780T2 (de) * 1995-12-20 2000-08-03 E.I. Du Pont De Nemours And Co., Wilmington Jod-enthaltende nitrile als kettenübertrager zur herstellung von perfluoropolymeren
TW494125B (en) * 1997-07-11 2002-07-11 Rohm And Haas Compary Preparation of fluorinated polymers
JP3721772B2 (ja) * 1998-03-06 2005-11-30 ユニマテック株式会社 撥水撥油剤
US6353051B1 (en) 1999-03-10 2002-03-05 E. I. Du Pont De Nemours And Company Top coating for synthetic leathers
US6761431B2 (en) 1999-12-13 2004-07-13 Canon Kabushiki Kaisha Polymer film, polymeric compound for forming the same, method of manufacturing such polymeric compound, liquid-repellency treatment solution using such polymeric compound, surface-modifying method using such treatment solution and surface-modified article
ITMI20031104A1 (it) 2003-06-03 2004-12-04 Solvay Solexis Spa Acidi carbossilici(per) fluoropolieterei e loro uso per il trattamento oleorepellente della carta
DE102005003262A1 (de) * 2005-01-24 2006-08-03 Albert-Ludwigs-Universität Freiburg Verwendung antimikrobieller Polymere als Emulgatoren und Emulgatoren enthaltende antimikrobielle Polymer-Dispersionen
EP1976820B1 (fr) * 2006-01-10 2010-09-29 Clariant Finance (BVI) Limited Composés télomères fluorés et polymères les contenant
JP4908013B2 (ja) * 2006-02-23 2012-04-04 株式会社サム技研Ｉｉ テープ付封筒の封緘装置
JP4908009B2 (ja) * 2006-02-10 2012-04-04 株式会社サム技研Ｉｉ テープ付封筒のテープ剥離装置
WO2008149676A1 (fr) * 2007-05-30 2008-12-11 Asahi Glass Company, Limited Composition d'agent antitache, procédé de production de celle-ci et article traité avec celle-ci
CN101508755B (zh) * 2009-03-11 2011-07-20 陕西科技大学 交联型自乳化阳离子全氟共聚物无皂乳液及其制备方法
CN102675534A (zh) * 2012-05-17 2012-09-19 陕西科技大学 超声辅助法制备阳离子氟碳改性聚丙烯酰胺

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4064091A (en) * 1974-08-09 1977-12-20 The Kendall Co. Process of forming a polymeric emulsion which comprises copolymerizing in aqueous dispersion an ethylenically-unsaturated monomer containing quaternary nitrogen
US4147851A (en) * 1978-06-13 1979-04-03 E. I. Du Pont De Nemours And Company Fluorine-containing oil- and water-repellant copolymers
US4504605A (en) * 1982-12-20 1985-03-12 The Standard Oil Company Film-forming olefinic nitrile polymer latex and method of preparing same
DE3407361A1 (de) * 1984-02-29 1985-08-29 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von hydrophobier- und oleophobiermittel

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0572269A1 (fr) * 1992-05-29 1993-12-01 Hoechst Gosei K.K. Composition aqueuse contenant du fluor, ayant des propriétés oléophobes et hydrophobes
US5346949A (en) * 1992-05-29 1994-09-13 Hoechst Gosei K.K. Fluorine containing aqueous composition having water repellent and oil repellent properties

Also Published As

Publication number Publication date
EP0345552B1 (fr) 1993-11-18
DE58906192D1 (de) 1993-12-23
EP0345552A3 (fr) 1991-03-27
JPH0243210A (ja) 1990-02-13
DE3842539A1 (de) 1989-12-21
US4997873A (en) 1991-03-05

Similar Documents

Publication Publication Date Title
EP0345552B1 (fr) Copolymères contenant des groupes perfluoralkyl
EP0552630B1 (fr) Copolymères contenant du fluor et dispersions aqueuses préparés de ces copolymères
DE19524345C2 (de) Schlichtemittel und deren Verwendung für Glasfasern
DE69316443T2 (de) Fluorhaltige wässrige Zusammensetzung für die Hydro- und Oleophobierung von Textilien
EP0424765B1 (fr) Dispersions de copolymérisats contenant des groupes perfluoroalkyles
DE3782865T2 (de) Pfropfcopolymer mit einem stabilisationseffekt fuer dispersionen, dessen herstellungsverfahren und verfahren fuer eine emulsionspolymerisation mit diesem stabilisiermittel.
EP0080635B1 (fr) Dispersion de polymère aqueuse auto-réticulante
DE1111394B (de) Verfahren zur Herstellung von Pfropfpolymerisaten
DE2103898A1 (de) Quaternare Copolymere
DE2749386A1 (de) Dispersionen hydrophiler acrylharze
EP0727441B1 (fr) Procédé de préparation de dispersion aqueuses de polymères sans émulsifiant
DE1445396A1 (de) Verfahren zur Herstellung von Mischpolymeren
DE3407361A1 (de) Verfahren zur herstellung von hydrophobier- und oleophobiermittel
EP0315876A2 (fr) Dispersion de copolymères à base de monomères insaturés éthyléniquement contenant des groupes uréthanes, leur procédé de préparation et leur utilisation
EP0160257B1 (fr) Copolymères contenant du fluor, procédé pour leur préparation et leur utilisation
EP0452774A2 (fr) Polymères greffés comprenant des groupes perfluoroalkyles
DE2738872A1 (de) Nichtionische oberflaechenaktive mittel aus acrylamid-mischpolymerisaten
DE2709503C2 (de) Stabile wässrige, emulgier- und dispergiermittelfreie Emulsion eines Acrylnitrilpolymerisats, Verfahren zu ihrer Herstellung und deren Verwendung als Mittel zur Verbesserung der Anfärbbarkeit
DE3800845A1 (de) Pfropfcopolymerisate, ein verfahren zu deren herstellung und deren verwendung
EP0661305A1 (fr) Dispersions aqueuses de résines synthétiques contenant pas de formaldéhyde
EP1658314B1 (fr) Utilisation d'acide 2-hydroxy-2-sulfinato-acetique ou de ses sels en tant qu'initiateur dans des emulsions eau dans l'huile
EP0364772A2 (fr) Copolymères contenant des groupes perfluoralkyl
WO1991008235A1 (fr) Production de dispersions polymeres stables avec des polymeres amphoteres comme stabilisant
DE69119134T2 (de) Wässrige Emulsionspolymere, hergestellt mit vernetzbaren nichtionischen Emulgiermitteln
EP0469429A2 (fr) Solutions aqueuses adhésifs sans solvant organique

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19890602

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): CH DE FR GB LI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): CH DE FR GB LI

17Q First examination report despatched

Effective date: 19921021

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR GB LI

REF Corresponds to:

Ref document number: 58906192

Country of ref document: DE

Date of ref document: 19931223

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19931130

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940414

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19940525

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19940531

Ref country code: CH

Effective date: 19940531

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19940525

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19950131

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960201